Crystal structure of N-[(naphthalen-1-yl)carbamo­thio­yl]cyclo­hexa­necarboxamide

G Vimala; J Haribabu; S Aishwarya; R Karvembu; A SubbiahPandi

doi:10.1107/S2056989015011950

. 2015 Jun 27;71(Pt 7):o508–o509. doi: 10.1107/S2056989015011950

Crystal structure of N-[(naphthalen-1-yl)carbamothioyl]cyclohexanecarboxamide

G Vimala ^a, J Haribabu ^b, S Aishwarya ^b, R Karvembu ^b, A SubbiahPandi ^a,^*

PMCID: PMC4518972 PMID: 26279935

Abstract

The title compound, C₁₈H₂₀N₂OS, displays whole-molecule disorder over two adjacent sets of sites with an occupancy ratio of 0.630 (11):0.370 (11). In each disorder component, the cyclohexyl ring shows a chair conformation with the exocyclic C—C bond in an equatorial orientation. The dihedral angles between the cyclohexyl ring (all atoms) and the naphthyl ring system are 36.9 (6) for the major component and 20.7 (12)° for the minor component. Each component features an intramolecular N—H⋯O hydrogen bond, which closes an S(5) ring. In the crystal, inversion dimers linked by pairs of N—H⋯S hydrogen bonds generate R ² ₂(8) loops for both components. Aromatic π–π stacking interactions [shortest centroid–centroid separation = 3.593 (9) Å] and a C—H⋯π interaction are also observed.

Keywords: crystal structure, whole-molecule disorder, thiourea derivatives, intramolecular N—H⋯O hydrogen bond, N—H⋯S hydrogen bonds, π–π stacking interactions, C—H⋯π interactions

Related literature

For background to the varied properties of thiourea derivatives, see: Sun et al. (2006 ▸); Shen et al. (2006 ▸). For related structures, see: Hu et al. (2011 ▸); Gangadharan et al. (2015 ▸). graphic file with name e-71-0o508-scheme1.jpg

Experimental

Crystal data

C₁₈H₂₀N₂OS
M _r = 312.42
Triclinic,
a = 7.0464 (5) Å
b = 11.0379 (5) Å
c = 12.4151 (8) Å
α = 110.873 (3)°
β = 100.660 (3)°
γ = 104.022 (3)°
V = 835.24 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▸) T _min = 0.934, T _max = 0.952
14064 measured reflections
2945 independent reflections
1930 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.068
wR(F ²) = 0.219
S = 1.05
2945 reflections
404 parameters
1056 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▸); cell refinement: SAINT (Bruker, 2004 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015011950/hb7448sup1.cif

e-71-0o508-sup1.cif^{(28.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015011950/hb7448Isup2.hkl

e-71-0o508-Isup2.hkl^{(144.5KB, hkl)}

Click here for additional data file.^{(6.1KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015011950/hb7448Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989015011950/hb7448fig1.tif

The molecular structure of the major component of the title compound, with displacement ellipsoids drawn at 40% probability level.

Click here for additional data file.^{(1MB, tif)}

. DOI: 10.1107/S2056989015011950/hb7448fig2.tif

Stick plot of both major and minor components of the title compound, with the atoms label for non-H atoms.

Click here for additional data file.^{(2.2MB, tif)}

b . DOI: 10.1107/S2056989015011950/hb7448fig3.tif

The crystal packing of the title compound, viewed along the b axis. The hydrogen bonds are shown as dashed lines (see Table 1 for details).

CCDC reference: 1408027

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

Cg1 is the centroid of the C1C5/C10 ring.

DHA	DH	HA	D A	DHA
N2H2AO1	0.88(4)	1.97(4)	2.667(15)	135(4)
N2H2AO1	0.93(4)	2.03(4)	2.62(3)	120(4)
N1H1AS1ⁱ	0.87(3)	2.53(3)	3.370(19)	161(4)
N1H1AS1ⁱ	0.90(4)	2.59(4)	3.44(3)	159(4)
C18H18B Cg1ⁱⁱ	0.90	2.66	3.527(2)	148

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the data collection. JH thanks UGC for the fellowship.

supplementary crystallographic information

S1. Comment

The design and synthesis of thiourea are of considerable interest because of their use in agriculture, medicine and analytical chemistry (J·H. Hu et al., 2011). Thiourea derivatives are driven by their potential as biological active compounds (Sun et al., 2006) and in the material application such as anti corrosion (Shen et al., 2006). As part of our own studies in this area, the crystal structure of the title compound has been determined and the results are presented herein.

For the major disorder component, the cyclohexane ring (C13—C18) adopts chair conformation [puckering amplitudes and smallest displacement parameters are q = 0.568 Å, θ = 177.7 (8)°, φ = 19 (29)° and ΔC_s = 0.9 (14) Å]. Similarly, for the minor disorder component, the cyclohexane ring (C13^'—C18^') adopts a chair conformation. [puckering amplitudes and smallest displacement parameters are q = 0.56 (3) Å, θ = 180 (3)°, φ = 354 (31)° and ΔC_s = 3.0 (4) Å]. The dihedral angles between cyclohexane and benzene rings (C5—C8/C10) and (C5—C10) of naphthalene moiety are 37.0 (7)and 36.5 (7)° (major component). In the case of minor component, the dihedral angles between cyclohexane and benzene rings (C5—C8/C10)and (C5—C10) of naphthalene are 37.0 (7)and 36.5 (7)°, respectively. The molecular conformation is consolidated by an intramolecular N—H···O hydrogen bond, forming S(5) ring motif.

The crystal packing features N—H···S hydrogen bonds with the symmetry code: (i) 2 - x,-y,1 - z, which links the molecules into centrosymmetric dimers with graph-set descriptor of R²₂(8). The crystal packing also features C—H···π (Table 1) and π-π interactions (Cg2···Cg2ⁱⁱ = 3.593 (9) Å; Cg2 is the centroid of a ring C5—C10; symmetry code: (ii) 3 - x,1 - y,2 - z. The packing view of the title compound is shown in Fig. 3.

S2. Experimental

A solution of cyclohexane carbonyl chloride (1.4661 g, 10 mmol) in acetone (60 ml) was added drop wise to a suspension of potassium thiocyanate (0.9718 g, 10 mmol) in anhydrous acetone (60 ml). The reaction mixture was heated under reflux for 45 minutes and then cooled to room temperature. A solution of substituted naphthalen-1-amine (1.43 g, 10 mmol) in acetone (60 ml) was added and the resulting mixture was stirred for 2 h at room temperature. Hydrochloric acid (0.1 N, 500 ml) was added and the resulting white solid was filtered off, washed with water and dried in vaccum. The yield of the isolated product was 89%, giving colourless blocks.